Cyclobutyl phosphate and phosphonate esters



United States Patent 3,485,898 CYCLOBUTYL PHOSPHATE AND PHOSPHONATE ESTERS Gerald H. Peterson, West Los Angeles, Calif. (12612 Preston Way, Los Angeles, Calif. 90066) 5 No Drawing. Filed Apr. 20, 1967, Ser. No. 632,320 Int. Cl. C07f 9/12, 9/40; C10m 3/40 US. Cl. 260958 14 Claims These new chemical compounds are useful for thermally stable fire resistant hydraulic fluids, especially for aircraft, either alone or admixed with other additives.

These compounds particularly include the following:

(1) Phosphate esters Tricyclobutyl phosphate Dicyclobutyl phenyl phosphate Monocyclobutyl diphenyl phosphate Dicyclobutyl tolyl phosphate Monocyclobutyl ditolyl phosphate Monocyclobutyl tolyl phenyl phosphate (2) Phosphonate esters Dicyclobutyl cyclobutane phosphonate Dicyclobutyl benzene phosphonate Diphenyl cyclobutane phosphonate Dicyclobutyl toluene phosphonate Ditolyl cyclobutane phosphonate Monocyclobutyl tolyl benzene phosphonate Monocyclobutyl phenyl toluene phosphonate The phosphonate esters particularly include the following:

Dicyclobutyl cyclobutane phosphonate Herein CB stands for the cyclobutyl radical.

Diphenyl cyclobutane phosphonate I Ph Herein Ph stands for the phenyl radical. 6O

Dimetatolyl cyclobutane phosphonate I. Tmeta Herein T stands for the tolyl radical and generically designates ortho, meta, and para tolyl and mixtures thereof.

3,485,898 Patented Dec. 23, 1969 Cyclobutyl metatolyl cyclobutane phosphonate OB 0=1 0Tm Herein Tm designates the metatolyl radical.

Cyclobutyl phenyl cyclobutane phosphonate CB 0=II0CB Dicyclobutyl benzene phosphonate Ph 0=1|0CB Dicyclobutyl toluene phosphonate Cyclobutyl phenyl benzene phosphonate Cyclobutyl metatolyl benzene phosphonate Cyclobutyl tolyl toluene phosphonate Cyclobutyl phenyl toluene phosphonate I CB Tolyl phenyl cyclobutane phosphonate (3B O= i0Tm I Ph Each of these new foregoing chemical compounds can be made by the same methods used for making the corresponding phosphates and phosphonates where the butyl radical is used instead of the cyclobutyl radical. The methods of making the corresponding phosphates and phosphonates with the butyl radical are known to those skilled in the art, and with the disclosure herein those skilled in the art to which my invention appertains will be able to make and use the new chemical compounds of my invention.

The preparation of the known phosphate esters and phosphonate esters having the butyl radical instead of the cyclobutyl radical of my invention is disclosed in the books entitled Introduction to Hydraulic Fluids by Roger E. Hatton, published by Rheinhold Publishing Corporation and Organo-Phosphorous Compounds by G. M. Kosolopofif, published by John Wiley and Sons, and numerous other publications and issued patents. The particular relevant disclosure in the book entitled Introduction to Hydraulic Fluids appears on pages 190 through 195.

Even though those skilled in the art will be able to prepare and use the new chemical compounds of my invention, there is given below examples of these compounds and their preparation.

EXAMPLE 1 Tricyclobutyl phosphate 3.5 mols of cyclobutyl alcohol are added dropwise with stirring to one mol of phosphorus oxychloride (POCl at 25-35 C. The temperature is slowly brought up to about 65 C. and the pressure is slowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride. The mixture is then distilled and tricyclobutyl phosphate is collected boiling at about 160-165 C. at 15 mm./I-Ig.

EXAMPLE 2 Tricyclobutyl phosphate To 5 mols of cyclobutanol, three mols of freshly cut metallic sodium are added in small cubes about A with stirring and maintaining the temperature between 25 and 40 C. When reaction is complete as evidenced by cessation of bubbling, one mol of phosphorus oxychloride (POCl is added dropwise with stirring while maintaining the temperature at about 25-50 C. The reaction mixture is filtered to remove the precipitated sodium chloride and the filtrate is distilled and tricyclobutyl phosphate is collected boiling at about 160-165 C. at 15 mm./Hg.

EXAMPLE 3 Dicyclobutyl phenyl phosphate Two mols of cyclobutanol are added dropwise with stirring to one mol of POCl at -35 C. The temperature is slowly brought up to about 65 C. and the pressure slowly reduced to 50 mm./Hg to remove hydrogen chloride. Without further purification this mixture is added dropwise at 0-5 C. to a saturated solution of one mol of phenol in one mol of sodium hydroxide with good stirring. The mixture is allowed to rise in temperature to 25 C. with continued stirring. The resulting mixture is washed, dried and distilled to separate out the desired water insoluble dicyclobutyl phenyl phosphate. The boiling point of this phosphate is about 165-1'70 C. at 15 mm./Hg.

EXAMPLE 4 Dicyclobutyl tolyl phosphate Two mols of cyclobutanol are added dropwise with stirring to one mol of POCl at 25-35 C. the temperature is slowly brought up to about 65 C. and the pressure slowly reduced to 50 min/Hg to remove hydrogen chloride. Without further purification this mixture is added dropwise at 0-5 C. to a saturated solution of one mol of metacresol in one mol of sodium hydroxide with good stirring. The mixture is allowed to rise in temperature to 25 C. with continued stirring. The resulting mixture is washed, dried and distilled to separate out the desired water insoluble dicyclobutyl metatolyl phosphate. The boiling point of this phosphate is about 175-l80 C. at 15 mm./Hg.

EXAMPLE 5 Monocyclobutyl diphenyl phosphate One mol of cyclobutanol is added dropwise with stirring to one mol of POCl at 25-35 C. The temperature is slowly brought up to about 65 C. and the pressure slowly reduced to 50 mm./Hg to remove hydrogen chloride. Without further purification this mixture is added dropwise at 0-5 C. to a saturated solution of two mols of phenol in two mols of NaOH with good stirring. The mixture is allowed to rise in temperature to 25 C. with continued stirring. The resulting mixture is washed, dried and distilled to separate out the desired water insoluble monocyclobutyl diphenyl phosphate. The boiling point of this phosphate is about 170-175 C. at 15 mm./Hg.

EXAMPLE 6 Monocyclobutyl paratolyl phosphate One mol of cyclobutanol is added dropwise with stirring to one mol of POCl at 25-35 C. The temperature is slowly brought up to about 65 C. and the pressure slowly reduced to 50 mm./Hg to remove hydrogen chloride. Without further purification this mixture is added dropwise at 0-5 C. to a saturated solution of two mols of paracresol in two mols of NaOH with good stirring. The mixture is allowed to rise in temperature to 25 C. with continued stirring. The resulting mixture is washed, dried and distilled to separate out the desired water insoluble rnonocyclobutyl paratolyl phosphate. The boiling point of this phosphate is about 180-185 C. at 15 mm./I-lg.

EXAMPLE 7 Monocyclobutyl phenyl tolyl phosphate One mol of cyclobutanol is added dropwise with stirring to one mole of POCl at 25-35 C. The temperature is slowly brought up to about 65 C. and the pressure slowly reduced to 50 min/Hg to remove hydrogen chloride. Without further purification this mixture is added dropwise at O5 C. to a saturated solution of one mol of phenol in one mol of sodium hydroxide with good strring. The mixture is allowed to rise in temperature to 25 C. with continued stirring. The mixture is filtered and the filtrate is added dropwise, without further purification, at 05 C. to a saturated solution of one mol of metacresol in one mol of NaOH with good stirring. The mixture is allowed to rise in temperature with continued stirring. The resulting mixture is washed, dried and distilled to separate out the desired water insolu-ble monocyclobutyl phenyl metatolyl phosphate. The boiling point of this phosphate ester is about 175-180 C. at 15 rum/Hg.

EXAMPLE 8 Dicyclobutyl cyclobutane phosphonate Three mols of cyclobutanol are added dropwise with stirring to one mol of cyclobutane phosphorus oxydichloride (CH CHP(O)CI at 25-35 C. The temperature is slowly brought up to about 65 C. and the pressure is slowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride. The mixture is then distilled and dicyclobutyl cyclobutane phosphonate is collected boiling at about -155 C. at 15 mm./Hg.

EXAMPLE 9 Diphenyl cyclobutane phosphonate Three mols of phenol are added dropwise with stirring to one mol of cyclobutane phosphorus oxydichloride at 2535 C. The temperature is slowly brought up to about 65 C. and the pressure is slowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride. The mixture is then distilled and diphenyl cyclobutane phosphonate is collected boiling at about -160 C. at 15 mm./Hg.

EXAMPLE 10 dimetatolyl cyclobutane phosphonate Three mols of metacresol are added dropwise with stirring to one mol of cyclobutane phosphorus oxydichloride at 25-35 C. The temperature is slowly brought up to about 65 C. and the pressure is slowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride. The mixture is then distilled and dimetatolyl cyclobutane phosphonate is collected boiling at about 155-160 C. at mm./Hg.

EXAMPLE 11 Cyclobutyl metatolyl cyclobutane phosphonate One mol of cyclobutanol is added dropwise with stirring to one mol of cyclobutane phosphorus oxydichloride at 2535 C. The temperature is slowly brought up to about 65 C. and the pressure is slowly reduced to 50 mm./Hg

EXAMPLE l2 Cyclobutyl phenyl cyclobutane phosphonate One mol of cyclobutanol is added dropwise with stirring to one mol of cyclobutane phosphorus oxydichloride at 25-35 C. The temperature is slowly brought up to about 60 C. and the pressure is slowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride. Without further purification this mixture is added dropwise at 0-5 C. to a saturated solution of one mol of phenol in one mol of sodium hydroxide with good stirring. The mixture is allowed to rise in temperature to 25 C. with continued stirring. The resulting mixture is washed, dried and distilled to separate out the desired water insoluble cyclobutyl phenyl cyclobutane phosphonate. The boiling point of this phosphonate is about 155160 C. at 15 mm./Hg.

EXAMPLE l3 Dicyclobutyl benzene phosphonate Three mols of cyclobutanol are added dropwise with stirring to one mol of benzene phenyl phosphorus oxydichloride at 2535 C. The temperature is slowly brought up to about 65 C. and the pressure is slowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride. The mixture is then distilled and dicyclobutyl benzene phosphonate is collected boiling at about l55-160 C. at 15 mm./Hg.

EXAMPLE 14 Dicyclobutyl toluene phosphonate Three mols of cyclobutanol are added dropwise with stirring to one mol of metatoluene phosphorus oxydichloride at 25-35 C. The temperature is slowly brought up to about 65 C. and the pressure is slowly reduced to 50 min/Hg with stirring to remove hydrogen chloride. The mixture is then distilled and dicyclobutyl toluene phosphonate is collected boiling at about 160-165 C. at 15 rum/Hg.

EXAMPLE 15 Cyclobutyl phenyl benzene phosphonate One mol of cyclobutanol is added dropwise with stirring to one mol of benzene phosphorus oxydichloride at 25-35 C. The temperature is slowly brought up to about 65 C. and the pressure is slowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride. Without further purification this mixture is added dropwise at 0-5 C. to a saturated solution of one mol of phenol in one mol of sodium hydroxide with good stirring. The mixture is allowed to rise in temperature to 25 C. with continued stirring. The mixture is Washed, dried and distilled and cyclobutyl phenyl benzene phosphonate is collected boiling at about 155160 C. at 15 min/Hg.

6 EXAMPLE 16 Cyclobutyl metatolyl benzene phosphonate One mol of cyclobutanol is added dropwise with stirring to one mol of benzene phosphorus oxydichloride at 25- 35C. The temperature is slowly brought up to about 65 C. and the pressure is slowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride. Without further purification this mixture is added dropwise at 0-5 C. to a saturated solution of one mol of metacresol in one mol of sodium hydroxide with good stirring. The mixture is allowed to rise in temperature to 25 C. with continued stirring. The mixture is Washed, dried and distilled and cyclobutyl metatolyl benzene phosphonate is collected boiling at about l60165 C. at 15 min/Hg.

EXAMPLE 17 Cyclobutyl tolyl toluene phosphonate One mol of cyclobutanol is added dropwise with stirring to one mol of metatoluene phosphorus oxydichloride at 2535 C. The temperature is slowly brought up to about 65 C. and the pressure is slowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride. Without further purification this mixture is added dropwise at 05 C. to a saturated solution of one mol of metacresol in one mol of sodium hydroxide with good stirring. This mixture is allowed to rise in temperature to 25 C. with continued stirring. The mixture is Washed, dried and distilled and cyclobutyl tolyl toluene phosphonate is collected boiling at about 165-170" C. at 15 mm./Hg.

EXAMPLE 18 Cyclobutyl phenyl toluene phosphonate One mol of cyclobutanol is added dropwise with stirring to one mol of metatoluene phosphorus oxydichloride at 25-35 C. The temperature is slowly brought up to about 65 C. and the pressure is slowly reduced to 50 mm./ Hg with stirring to remove hydrogen chloride. Without further purification this mixture is added dropwise at 0-5 C. to a saturated solution of one mol of phenol in one mol of sodium hydroxide with good stirring. This mixture is allowed to rise in temperature to 25 C. with continued stirring. The mixture is washed, dried and distilled and cyclobutyl phenyl toluene phosphonate is collected boiling at about -165 C. at 15 mm./Hg.

EXAMPLE 19 Tolyl phenyl cyclobutane phosphonate One mol of metacresol is added dropwise with stirring to one mol of cyclobutane phosphorus oxydichloride at 25-35 C. The temperature is slowly brought up to about 65 C. and the pressure is slowly reduced to 50 mm./Hg with stirring to remove hydrogen chloride. Without further purification this mixture is added dropwise at 05 C. to a saturated solution of one mol of phenol in one mol of sodium hydroxide with good stirring. This mixture is allowed to rise in temperature to 25 C. with continued stirring. The mixture is Washed, dried and distilled and tolyl phenyl cyclobutane phosphonate is collected boiling at about 160-165 C. at 15 min/Hg.

The compositions of my invention have high thermal stability apparently due to the presence of the cyclobutyl radical, high fire resistance, good lubricity, especially hydrodynamic lubricity, good boundary lubrication and good anti-wear, have ability to lubricate moving parts, particularly steel on steel, good viscosity and viscositytemperature properties, and are readily admixed with many additives.

It will be understood that the specific embodiments of my invention described above are intended to illustrate and exemplify my invention and are not necessarily intended as a limitation thereon and that modifications of my invention may be made.

I claim:

1. The phosphate and phosphonate esters represented by the formula (R R R )O O PO in which x may be one or zero, R is cyclobutyl, and R and R are cyclobutyl, phenyl or tolyl.

2. The chemical compound as defined in claim 1 which is tricyclobutyl phosphate.

3. The chemical compound as defined in claim 1 which is dicyclobutyl cyclobutane phosphonate.

4. The chemical compound as defined in claim 1 which is dicyclobutyl phenyl phosphate.

5. The chemical compound as defined in claim 1 which is dicyclobutyl benzene phosphonate.

6. The chemical compound as defined in claim 1 which is dicyclobutyl tolyl phosphate.

7. The chemical compound as defined in. claim 1 which is dicyclobutyl toluene phosphonate.

8. The chemical compound as defined in claim 1 which is monocyclobutyl diphenyl phosphate.

9. The chemical compound as defined in claim 1 which is monocyclobutyl phenyl benzene phosphonate.

10. The chemical compound as defined in claim 1 which is monocyclobutyl ditolyl phosphate.

11. The chemical compound as defined in claim 1 which is monocyclobutyl tolyl toluene phosphonate.

12. The chemical compound as defined in claim 1 which is monocyclobutyl tolyl phenyl phosphate.

13. The chemical compound as defined in claim 1 which is monocyclobutyl tolyl benzene phosphonate.

14. The chemical compound as defined in claim 1 which is monocyclobutyl phenyl toluene phosphonate.

References Cited UNITED STATES PATENTS 1,959,228 5/ 1934- Blagden et a1. 260958 XR 2,682,522 6/1954 Coover et a1. 260-958 XR CHARLES B. PARKER, Primary Examiner A. H. SUTTO, Assistant Examiner US. Cl. X.R. 

